Separation Methods Utilizing Oxalate‐HCl on Anion Exchange Resins Dan McAlister and Phil Horwitz Eichrom Workshop October 31, 2012
Separation Methods Utilizing Oxalate‐HCl on Anion Exchange ResinsDan McAlister and Phil Horwitz
Eichrom Workshop October 31, 2012
CH2
HC
CH2N+
CH3
CH3
CH3 Cl-
Anion Exchangers
N+R1R2
R3
CH3
Cl-
NR1
R2R3
H+Cl-
Strong Base Anion Exchange Resin (1x8)1.2 meq/mL
TEVA(Quaternary Amine)
0.65 meq/mL
Weak Base(Tertiary Amine)0.65 meq/mL
Anion Exchange
TcO4‐, ReO4
‐, MoO42‐, WO4
2‐
Th(NO3)5‐, UO2Cl42‐, FeCl4‐
O O
O--OStrelow, et al., Analytical Chemistry, 44(14), pp 2352‐2356, 1972.
+ HCl
101 100 10-1 10-2 10-3 10-4 10-5 10-60
20
40
60
80
100
% S
peci
es
[H+], M
Speciation of 0.05 M Oxalic Acid vs [H+]
O O
O--O
O O
O-HO
O O
OHHO
pKa1 = 1.2pKa2 = 3.7
O O
O--O
O O
O-HO
O O
OHHO
Increasing HCl Concentration
Mn+ → MCl → MClx‐
Chloride competition for extraction
Example #1
IonMetal Charge 1 2 3 1 2 3Mg 2+ 2.76 0.2Al 3+ 6.2 11.4 15.8 ‐1.0Ga 3+ 6.4 12.3 17.8 0.01 3.6 4.0In 3+ 6 11.4 14.5 2.3 11.4 14.5
Oxalate logK Chloride logK
10-2 10-1 100 10110-1
100
101
102
103
104
105
Dw Mg < 1Dw Mg < 1Dw Mg < 1
TEVAWeak Base1x8
Dw
HCl, M
In Ga Al
10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
0 5 10 15 20 25 30 3510-3
10-2
10-1
100
101
102
103
Elution on 2mL Cartridge of 1x8 Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
0.5M HCl
0.05MOxalate
1.0M HCl
1.0 MHNO3
InGaAl
Mg
m
g/L
Bed Volumes
0 5 10 15 20 25 30 3510-3
10-2
10-1
100
101
102
103
Elution on 2mL Cartridge of TEVA Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
0.5M HCl
0.05MOxalate
1.0M HCl
1.0 MHNO3
InGaAl
Mg
m
g/L
Bed Volumes
0 5 10 15 20 25 30 3510-3
10-2
10-1
100
101
102
103
Elution on 2mL Cartridge of Weak Base Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
0.5M HCl
0.05MOxalate
1.0M HCl
1.0 MHNO3
InGaAl
Mg
mg/
L
Bed Volumes
10-2 10-1 100 10110-1
100
101
102
103
104
105
U(VI) Nb(V) Ni(II) V(V)
Dw Ni and Mn < 1Dw Mn(II) < 1Dw Mn(II) < 1
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
Example #2
0 5 10 15 20 25 30 35 40 4510-3
10-2
10-1
100
101
102
103
0.05MOxalate
0.2M HCl
V(V)
Elution on 2mL Cartridge of 1x8 Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
1.0M HCl
0.05MOxalate
4.0M HCl
1.0 MHNO3
U(VI)
Nb(V)Mn(II)Ni(II)
mg/
L
Bed Volumes
0 5 10 15 20 25 30 35 40 4510-3
10-2
10-1
100
101
102
103
0.05MOxalate
0.2M HCl
V(V)
Elution on 2mL Cartridge of Weak Base Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
1.0M HCl
0.05MOxalate
4.0M HCl
1.0 MHNO3
U(VI)Nb(V)Mn(II)
Ni(II)
mg/
L
Bed Volumes
0 5 10 15 20 25 30 35 40 4510-3
10-2
10-1
100
101
102
103
0.05MOxalate
0.2M HCl
V(V)
Elution on 2mL Cartridge of TEVA Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
1.0M HCl
0.05MOxalate
4.0M HCl
1.0 MHNO3
U(VI)Nb(V)Mn(II)
Ni(II)
mg/
L
Bed Volumes
Example #3
10-2 10-1 100 10110-1
100
101
102
103
104
105
Cu(II) Ti(IV) Mo(VI)
Dw Co(II) < 1Dw Co(II) < 1Dw Co(II) < 1
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
0 5 10 15 20 25 30 35 4010-3
10-2
10-1
100
101
102
103
Elution on 2mL Cartridge of 1x8 Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
0.5M HCl
0.05MOxalate
2.0M HCl
0.5MNH4OH1.0 M
NH4NO3Cu(II)
Ti(IV)
Mo(VI)Co(II)
m
g/L
Bed Volumes
0 5 10 15 20 25 30 35 4010-3
10-2
10-1
100
101
102
103
Elution on 2mL Cartridge of Weak Base Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
0.5M HCl
0.05MOxalate
2.0M HCl
0.5MNH4OH1.0 M
NH4NO3Cu(II) Ti(IV)
Mo(VI)Co(II)
mg/
L
Bed Volumes
0 5 10 15 20 25 30 35 4010-3
10-2
10-1
100
101
102
103
Elution on 2mL Cartridge of TEVA Resin (50-100 m), 21(1)oC, 2mL/min
0.05MOxalate
0.01M HCl
0.05MOxalate
0.5M HCl
0.05MOxalate
2.0M HCl
0.5MNH4OH1.0 M
NH4NO3Cu(II) Ti(IV)
Mo(VI)Co(II)
m
g/L
Bed Volumes
10-2 10-1 100 10110-1
100
101
102
103
104
105
Dw Li, Na, K, Rb, Cs < 1
Dw Li, Na, K, Rb, Cs < 1
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
Dw Li, Na, K, Rb, Cs < 1
HCl, M
10-2 10-1 100 10110-1
100
101
102
103
104
105
Pd(II) Pt(II) Au(I) Pb(II)
Dw Mg, Ca, Sr, Ba, Mn(II) <1
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
Dw Mg, Ca, Sr, Ba, Mn(II) <1
HCl, M10-2 10-1 100 101
Dw Mg, Ca, Sr, Ba, Mn(II) <1
HCl, M
10-2 10-1 100 10110-1
100
101
102
103
104
105
Zn(II) Cu(II) Be(II) Cd(II)
Dw Be, Mg, Ca, Sr, Ba, Mn(II) <1
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
Dw Be, Mg, Ca, Sr, Ba, Mn(II) <1
HCl, M10-2 10-1 100 101
Dw Be, Mg, Ca, Sr, Ba, Mn(II) <1
HCl, M
10-2 10-1 100 10110-1
100
101
102
103
104
105
Bi(III) In(III) Fe(III) Ga(III) Al(III)
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
10-2 10-1 100 10110-1
100
101
102
103
104
105
Sn(IV) Ti(IV) Zr(IV) Hf(IV)
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
10-2 10-1 100 10110-1
100
101
102
103
104
105
Ta(V) Nb(V) V(V)
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
10-2 10-1 100 10110-1
100
101
102
103
104
105
W(VI) Mo(VI) U(VI)
TEVAWeak Base1x8
Dw
HCl, M10-2 10-1 100 101
HCl, M10-2 10-1 100 101
HCl, M
OxidationElement State Group 0.01 0.10 0.20 0.50 1.0 2.0 3.0 4.0
Sn IV 14 >104 >104 >104 >104 >104 >104 >104 >104
W VI 6 9800 9900 9600 9800 710 150 78 130Pd II 10 >104 >104 >104 >104 9500 5000 2500 1100Mo VI 6 >104 >104 >104 >104 >104 >104 >104 >104
Bi III 15 5000 5000 >104 >104 >104 >104 >104 >104
Pt II 10 >104 >104 >104 >104 >104 >104 >104 >104
Ta V 5 N/A 3400 5400 4500 4500 44 45 33Cd II 12 N/A 2100 3000 4000 3700 4900 4800 4900In III 13 8100 9000 8300 420 41 51 110 250Nb V 5 1200 1500 1000 870 91 5.8 2.3 1.4U VI An >104 >104 >104 >104 >104 180 8200 >104
Zn II 12 N/A 50 170 9000 920 >104 >104 >104
Ti IV 4 9300 2000 1400 380 130 12 1.8 0.8Fe III 8 N/A >104 >104 2600 19 200 >104 >104
Zr IV 4 N/A 6900 930 260 66 1.0 0.2 0.4Hf IV 4 N/A 1200 600 570 27 1.2 <0.5 <0.5Ga III 13 2000 1800 1100 140 4.3 92 970 1200Pb II 14 N/A 4.0 4.4 15 22 25 18 10V V 5 9486 1300 400 14 0.5 0.5 0.4 0.7Al III 13 7983 200 340 3.7 < 0.5 < 0.5 < 0.5 < 0.5Cu II 11 263 17 8.0 0.5 0.6 3.2 13 31Ni II 10 85 0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5Th IV An ppt ppt ppt ppt ppt 3.2 < 0.5 < 0.5Re VII 7 N/A >103 >103 >103 >103 >103 >103 >103
Cr III 6 N/A < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5Au I 11 2300 2800 2700 2300 1800 970 900 830
k' Co, Mn, Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs <0.5 for all HCl concentrations
k' on Weak Base Resin M, HCl (0.05M Oxalic acid)
OxidationElement State Group 0.01 0.10 0.20 0.50 1.0 2.0 3.0 4.0
Sn IV 14 N/A >104 >104 >104 >104 >104 >104 >104
W VI 6 9800 9600 9200 4900 510 110 40 45Pd II 10 9800 9200 9100 5000 4800 1300 450 180Mo VI 6 9600 9300 9200 9900 9600 5100 >104 >104
Bi III 15 5100 4800 >104 >104 >104 >104 >104 400Pt II 10 N/A >104 >104 >104 >104 >104 >104 >104
Ta V 5 N/A 2100 2200 3800 51 40 38 14Cd II 12 N/A 650 1200 2000 2900 4800 4100 4300In III 13 8300 250 180 38 16 25 47 78Nb V 5 1000 1500 1400 310 29 6.1 4.1 2.3U VI An 2100 2100 1300 130 23 70 350 >104
Zn II 12 N/A 48 100 320 450 7700 9300 4600Ti IV 4 2300 1400 870 300 90 6.7 1.5 0.4Fe III 8 N/A 6500 8800 45 4.3 130 1100 1100Zr IV 4 N/A 3800 2300 53 2.2 0.4 0.2 0.1Hf IV 4 N/A 6000 670 19 1.4 1.0 <0.5 <0.5Ga III 13 4200 3000 180 9.7 0.4 55 1500 3200Pb II 14 N/A 0.7 6.0 14 18 19 12 7.3V V 5 3000 310 55 4.7 0.4 0.4 0.6 1.3Al III 13 2700 110 16 0.7 < 0.5 < 0.5 < 0.5 < 0.5Cu II 11 18 2.2 0.7 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5Th IV An ppt ppt ppt ppt ppt 40 36 <0.5Re VII 7 N/A >103 >103 >103 >103 >103 >103 >103
Cr III 6 N/A < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5Au I 11 1400 3900 4500 4600 4600 3400 2300 2300
k' Co, Mn, Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs <0.5 for all HCl concentrations
k' on TEVA Resin M, HCl (0.05M Oxalic acid)